CN112076789A - Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt - Google Patents

Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt Download PDF

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CN112076789A
CN112076789A CN202010867847.5A CN202010867847A CN112076789A CN 112076789 A CN112076789 A CN 112076789A CN 202010867847 A CN202010867847 A CN 202010867847A CN 112076789 A CN112076789 A CN 112076789A
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佘远斌
王雄
宁磊
沈海民
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Zhejiang University of Technology ZJUT
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Abstract

A method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt comprises the steps of dispersing PCN-224(Co) (0.001% -10%, g/mol) and Zn (II) salt (0.01% -10%, mol/mol) in cycloalkane, sealing a reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and then carrying out aftertreatment on reaction liquid to obtain the product, namely, cycloalkanol and cycloalkanone. The method has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.

Description

Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt
Technical Field
The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by oxidizing cycloalkane under the concerted catalysis of metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt, belonging to the field of industrial catalysis and fine organic synthesis.
Background
Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important intermediates in fine chemical industry, and are widely used in synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins, and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, has the main problems of high reaction temperature, low substrate conversion rate, poor selectivity of the target product, and in particular, difficulty in inhibiting the formation of aliphatic diacids (Applied Catalysis a, general2019,575: 120-; catalysis Communications2019,132: 105809). The main sources of the above problems are: (1) at present, O is industrially used2Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled2The free radical diffusion in the process of catalytically oxidizing cycloalkane and the catalytic conversion of the intermediate product cycloalkyl hydroperoxide are beneficial to the improvement of the catalytic oxidation selectivity of cycloalkane, and the catalyst is a very important element in the field of catalytic oxidation of cycloalkane in industryNovel and application-significant process improvements.
The metal-organic framework material PCN-224 is a series of porous materials with better Chemical stability and thermal stability, which is applied to the field of organic catalysis, not only can realize the high-efficiency dispersion of catalytic active centers, but also can provide a certain micro-domain environment for Chemical reactions, effectively prevent the disordered diffusion of free radicals and improve the reaction selectivity (Journal of the American Chemical Society 2017,139: 18590-. In addition, Zn (II) can catalyze the decomposition and conversion of naphthenic base hydrogen peroxide which is an intermediate product of oxidation of naphthenic hydrocarbon, prevent the non-selective thermal decomposition and conversion of the naphthenic base hydrogen peroxide and improve the selectivity of catalytic oxidation of the naphthenic hydrocarbon (Catalysis communications2019,132: 105809).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by synergistically catalyzing and oxidizing cycloalkane with metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt, wherein the metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt is used as a binary catalyst to synergistically catalyze O2The method for selectively synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the naphthenic hydrocarbon has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less by-products, small environmental influence and the like, and the method provided by the invention has low content of naphthenic hydroperoxide and high safety factor, and is an efficient, feasible and safe method for selectively catalytically oxidizing the naphthenic hydrocarbon to synthesize the naphthenic alcohol and the naphthenic ketone.
The technical scheme of the invention is as follows:
a method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt, said method comprising the following steps:
dispersing metalloporphyrin MOFs PCN-224(Co) and Zn (II) salt into cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-224(Co) is 0.001% -10% of the mass of the cycloalkane, and the mass is g/mol; the amount of Zn (II) salt is 0.01-10% of that of cycloalkane, mol/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the metalloporphyrin MOFs PCN-224(Co) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
Figure BDA0002650231930000021
Figure BDA0002650231930000031
the Zn (II) salt is Zn (CH)3COO)2，Zn(NO3)2，ZnSO4，ZnCl2And hydrates thereof, preferably anhydrous Zn (CH)3COO)2；
The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
Further, the ratio of the mass of the metalloporphyrin MOFs PCN-224(Co) to the amount of substances of the cycloalkane is 1: 100000-1: 10, preferably 1: 10000-1: 10.
The mass ratio of Zn (II) salt to cycloalkane is 1: 10000-1: 10, preferably 1: 1000-1: 10.
The reaction temperature is 90-150 ℃, and preferably 100-130 ℃; the reaction pressure is 0.10-2.0 MPa, preferably 0.60-1.20 MPa; the stirring speed is 600-1200 rpm, preferably 800-1000 rpm.
The oxidant is oxygen, air or a mixture of oxygen and air in any proportion.
The post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 3 percent of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of the reaction liquid by triphenylphosphine is sampled and analyzed. Diluting with acetone as solvent, performing gas chromatography with toluene as internal standard, and calculating conversion rate of cycloalkane and selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid;
the invention constructs a binary catalytic system by using metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt to synergistically catalyze O2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the cycloalkane not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product naphthenic hydrogen peroxide, greatly improves the selectivity of the target product naphthenic alcohol and naphthenic ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing naphthenic alcohol and naphthenic ketone by efficiently and selectively oxidizing naphthenic C-H bonds, but also has certain reference value for efficiently preparing alcohol and ketone compounds by selectively catalyzing and oxidizing other hydrocarbon C-H bonds.
The invention has the following beneficial effects: the method for synthesizing the naphthenic alcohol and the naphthenic ketone by the synergistic catalytic oxidation of the metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrins MOFs PCN-224(Co) used in the present invention are all referred to Journal of the American Chemical Society 2017,139: 18590-18597; journal of the American Chemical Society 2013,135: 17105-17110; inorganic Chemistry 2019,58: 5145-. All reagents used were commercially available analytical grade.
Examples 1 to 3 are syntheses of the metalloporphyrins MOFs PCN-224 (Co).
Examples 4 to 36 are examples of catalytic oxidation of cycloalkanes.
Examples 37 to 42 are comparative experimental cases of catalytic oxidation of cycloalkanes.
Example 43 is a catalytic oxidation scale-up experimental case for cycloalkanes.
Example 1
(0.0847g,0.1mmol) T (4-COOH) PPCo (II), (0.1864g,0.8mmol) ZrCl was placed in a 35mL pressure tube42.4421g (20.0mmol) of benzoic acid is dissolved in 10mL of DMF, ultrasonic treatment is carried out for 10min to assist the dissolution, the temperature of a pressure-resistant tube is raised from room temperature to 120 ℃ in a constant-temperature oven, the reaction is carried out for 72.0h at the temperature, and brick-red solid is generated on the inner wall of the tube. And (3) turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower-layer solid, washing the solid by using N, N dimethylformamide (5X 6mL) and acetone (5X 6mL) respectively, taking the lower-layer brick-red solid, and drying the lower-layer brick-red solid at 60 ℃ for 8.0h to obtain 0.0312g of the target product PCN-224-p.
Example 2
(0.0847g,0.1mmol) T (3-COOH) PPCo (II), (0.1864g,0.8mmol) ZrCl was placed in a 35mL pressure tube42.4421g (20.0mmol) of benzoic acid is dissolved in 10mL of DMF, ultrasonic treatment is carried out for 10min to assist the dissolution, the temperature of a pressure-resistant tube is raised from room temperature to 120 ℃ in a constant-temperature oven, the reaction is carried out for 72.0h at the temperature, and brick-red solid is generated on the inner wall of the tube. And (3) turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower-layer solid, washing the solid by respectively using N, N dimethylformamide (5X 6mL) and acetone (5X 6mL), taking the lower-layer brick-red solid, and drying the lower-layer brick-red solid at 60 ℃ for 8.0h to obtain 0.0211g of a target product PCN-224-m.
Example 3
In a 35mL pressure tube, (0.1152g,0.1mmol) [ T (4- (4-COOH) P) PPCo (II) ]]，(0.1864g,0.8mmol)ZrCl42.4421g (20.0mmol) of benzoic acid in 10mLPerforming ultrasonic treatment for 10min in DMF to assist dissolution, heating the pressure-resistant pipe to 120 ℃ from room temperature in a constant-temperature oven, and reacting for 72.0h at the temperature, wherein brick-red solid is generated on the inner wall of the pipe. Turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower layer solid, washing the solid with N, N dimethylformamide (5X 6mL) and acetone (5X 6mL) respectively, taking the lower layer brick-red solid, and drying at 60 ℃ for 8.0h to obtain 0.0120g of the target product PCN-224-d.
Example 4
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.000002g PCN-224-d (Co) and 0.00367g (0.02mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.03%, cyclohexanol selectivity 34%, cyclohexanone selectivity 32%, cyclohexyl hydroperoxide selectivity 34%, no detectable formation of adipic acid and glutaric acid.
Example 5
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.00002g PCN-224-d (Co) and 0.00367g (0.02mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standardAnalyzing; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.53%, cyclohexanol selectivity 35%, cyclohexanone selectivity 38%, cyclohexyl hydroperoxide selectivity 27%, no formation of adipic acid and glutaric acid was detected.
Example 6
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.00367g (0.02mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 5.3%, the cyclohexanol selectivity was 51%, the cyclohexanone selectivity was 41%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 4%, and the formation of glutaric acid was not detected.
Example 7
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0180g PCN-224-d (Co) and 0.00367g (0.02mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.3%, cyclohexanol selectivity 53%, cyclohexanone selectivity 39%, cyclohexylThe hydrogen peroxide selectivity was 6% and the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 8
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0200g PCN-224-d (Co) and 0.00367g (0.02mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.83%, cyclohexanol selectivity 51%, cyclohexanone selectivity 40%, cyclohexyl hydroperoxide selectivity 7%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 9
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.0367g (0.20mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 7.53%, the cyclohexanol selectivity is 50%, the cyclohexanone selectivity is 40%, the cyclohexyl hydroperoxide selectivity is 6%, the adipic acid selectivity is 4%, and the formation of glutaric acid is not detected.
Example 10
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.5%, cyclohexanol selectivity 50%, cyclohexanone selectivity 46%, cyclohexyl hydroperoxide selectivity 2%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 11
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 3.6696g (20.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 7.63%, the cyclohexanol selectivity was 49%, the cyclohexanone selectivity was 41%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 6%, and the formation of glutaric acid was not detected.
Example 12
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Is dispersed in16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 100 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.03%, cyclohexanol selectivity 35%, cyclohexanone selectivity 29%, cyclohexyl hydroperoxide selectivity 34%, adipic acid selectivity 2%, no formation of glutaric acid was detected.
Example 13
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 110 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 110 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 2.16%, the cyclohexanol selectivity was 47%, the cyclohexanone selectivity was 30%, the cyclohexyl hydroperoxide selectivity was 20%, the adipic acid selectivity was 3%, and the formation of glutaric acid was not detected.
Example 14
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 90 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. Reaction ofAfter completion, the ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.53%, cyclohexanol selectivity 25%, cyclohexanone selectivity 21%, cyclohexyl hydroperoxide selectivity 54%, no formation of adipic acid and glutaric acid was detected.
Example 15
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 9.05%, the cyclohexanol selectivity is 35%, the cyclohexanone selectivity is 41%, the cyclohexyl hydroperoxide selectivity is 7%, the adipic acid selectivity is 12%, and the glutaric acid selectivity is 5%.
Example 16
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 150 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 150 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The acetone is used as a solvent, and the acetone is used as a solvent,the resulting reaction mixture was taken to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 15.83%, the cyclohexanol selectivity is 23%, the cyclohexanone selectivity is 46%, the cyclohexyl hydroperoxide selectivity is 6%, the adipic acid selectivity is 18%, and the glutaric acid selectivity is 7%.
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 0.1 MPa. Stirring and reacting at 120 ℃ and 0.1MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.73%, cyclohexanol selectivity 26%, cyclohexanone selectivity 26%, cyclohexyl hydroperoxide selectivity 48%, no detectable formation of adipic acid and glutaric acid.
Example 18
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 0.6 MPa. Stirring and reacting at 120 ℃ and 0.6MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and liquid chromatography was performed using benzoic acid as an internal standardAnd (4) performing spectrum analysis. Cyclohexane conversion 4.73%, cyclohexanol selectivity 47%, cyclohexanone selectivity 45%, cyclohexyl hydroperoxide selectivity 6%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 19
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.57%, cyclohexanol selectivity 44%, cyclohexanone selectivity 49%, cyclohexyl hydroperoxide selectivity 5%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 20
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.4 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.4MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.62%, cyclohexanol selectivity 42%, cyclohexanone selectivity 49%, cyclohexyl hydroperoxide selectivity 7%, adipic acid selectivity 2%, not detectedTo glutaric acid formation.
Example 21
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.6 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.7%, the cyclohexanol selectivity was 40%, the cyclohexanone selectivity was 54%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 22
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 2.0 MPa. Stirring and reacting at 120 ℃ and 2.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.82%, the cyclohexanol selectivity was 38%, the cyclohexanone selectivity was 56%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 23
Stainless steel high pressure reactor with polytetrafluoroethylene inner container in 100mLInto the autoclave were charged 0.0140g of PCN-224-d (Co) and 0.3670g (2.0mmol) of Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 7.43%, the cyclohexanol selectivity was 48%, the cyclohexanone selectivity was 41%, the cyclohexyl hydroperoxide selectivity was 9%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 24
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 900rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 8.59%, the cyclohexanol selectivity was 46%, the cyclohexanone selectivity was 48%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 25
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating toOxygen was introduced at 120 ℃ to 1.0 MPa. The reaction was stirred at 1200rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.77%, the cyclohexanol selectivity was 40%, the cyclohexanone selectivity was 54%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 26
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 2.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.27%, cyclohexanol selectivity 20%, cyclohexanone selectivity 24%, cyclohexyl hydroperoxide selectivity 56%, no detectable formation of adipic acid and glutaric acid.
Example 27
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 6.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice-water, and 1.3115g (5.00mmol) of the mixture was added) Triphenylphosphine (PPh)3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 5.27%, the cyclohexanol selectivity was 40%, the cyclohexanone selectivity was 44%, the cyclohexyl hydroperoxide selectivity was 15%, the adipic acid selectivity was 1%, and the formation of glutaric acid was not detected.
Example 28
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 10.87%, the cyclohexanol selectivity is 36%, the cyclohexanone selectivity is 48%, the cyclohexyl hydroperoxide selectivity is 4%, the adipic acid selectivity is 10%, and the glutaric acid selectivity is 2%.
Example 29
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 24.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removedTaking methylbenzene as an internal standard to carry out gas chromatography analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 16.33%, the cyclohexanol selectivity is 30%, the cyclohexanone selectivity is 33%, the cyclohexyl hydroperoxide selectivity is 4%, the adipic acid selectivity is 22%, and the glutaric acid selectivity is 11%.
Example 30
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing air to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa air pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 3.27%, the cyclohexanol selectivity was 40%, the cyclohexanone selectivity was 34%, the cyclohexyl hydroperoxide selectivity was 24%, the adipic acid selectivity was 2%, and no formation of glutaric acid was detected.
Example 31
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-p (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.02%, cyclohexanolThe selectivity was 51%, the selectivity for cyclohexanone was 43%, the selectivity for cyclohexyl hydroperoxide was 4%, the selectivity for adipic acid was 2%, and the formation of glutaric acid was not detected.
Example 32
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-m (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.83%, cyclohexanol selectivity 52%, cyclohexanone selectivity 42%, cyclohexyl hydroperoxide selectivity 4%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 33
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 14.0260g (200mmol) of cyclopentane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 4.54%, the selectivity of cyclopentanol was 50%, the selectivity of cyclopentanone was 46%, the selectivity of cyclopentyl hydroperoxide was 3%, and the selectivity of glutaric acid was 1%, and no formation of succinic acid was detected.
Example 34
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 19.6380g (200mmol) of cycloheptane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 25.25 percent, the selectivity of cycloheptanol is 51 percent, the selectivity of cycloheptanone is 45 percent, the selectivity of cycloheptyl hydroperoxide is 3 percent, the selectivity of pimelic acid is 1 percent, and the generation of adipic acid is not detected.
Example 35
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 22.4440g (200mmol) of cyclooctane, sealing the reaction kettle, stirring, heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclooctane is 32.23%, the selectivity of cyclooctanol is 52%, the selectivity of cyclooctanone is 45%, the selectivity of cyclooctyl hydrogen peroxide is 2%, the selectivity of suberic acid is 1%, and the generation of pimelic acid is not detected.
Example 36
0.0140g of PCN-224-d (Co) and 0.3670 were placed in a 100mL stainless steel autoclave having a Teflon linerg(2.0mmol)Zn(CH3COO)2Dispersing in 16.8451g (100.0mmol) of cyclododecane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 34.51%, the selectivity for cyclododecanol was 51%, the selectivity for cyclododecanone was 45%, and the selectivity for cyclododecyl hydroperoxide was 4%, and no formation of acid was detected.
Example 37
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0029g [ T (4- (4-COOMe) P) PPCo (II) ]]Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.45%, the cyclohexanol selectivity is 41%, the cyclohexanone selectivity is 38%, the cyclohexyl hydroperoxide selectivity is 6%, the adipic acid selectivity is 10%, and the glutaric acid selectivity is 5%.
Example 38
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0027g [ T (4- (4-COOH) P) PPCo (II) ]]Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water1.3115g (5.00mmol) of triphenylphosphine (PPh) were added3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.59%, cyclohexanol selectivity 29%, cyclohexanone selectivity 16%, cyclohexyl hydroperoxide selectivity 48%, adipic acid selectivity 7%, and no formation of glutaric acid was detected.
Example 39
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.3670g (2.0mmol) Zn (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.92%, the cyclohexanol selectivity is 27%, the cyclohexanone selectivity is 35%, the cyclohexyl hydroperoxide selectivity is 20%, the adipic acid selectivity is 14%, and the glutaric acid selectivity is 4%.
Example 40
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.5950g (2.0mmol) Zn (NO)3)2·6H2O is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed as aPerforming gas chromatography with benzene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.61%, the cyclohexanol selectivity is 26%, the cyclohexanone selectivity is 34%, the cyclohexyl hydroperoxide selectivity is 21%, the adipic acid selectivity is 15%, and the glutaric acid selectivity is 4%.
EXAMPLE 41
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.2726g (2.0mmol) Zn (Cl)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.57%, the cyclohexanol selectivity is 30%, the cyclohexanone selectivity is 34%, the cyclohexyl hydroperoxide selectivity is 18%, the adipic acid selectivity is 13%, and the glutaric acid selectivity is 5%.
Example 42
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.3229g (2.0mmol) of ZnSO was placed4Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.32%, cyclohexanol selectivity 28%, cyclohexanone selectivity 35%, cyclohexyl hydroperoxide selectivity 17%, adipic acid selectivity14% and selectivity to glutaric acid 6%.
Example 43
In a 1.00L stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.1200g of PCN-224-d (Co) and 3.6696g (2.0mmol) of Zn (CH)3COO)2Dispersing in 168.32g (2.00mol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.1145g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Distilling, recovering 155.01g of cyclohexane, wherein the conversion rate is 7.91%; vacuum rectification is carried out to obtain 6.3901g of cyclohexanol with selectivity of 48 percent, 6.1245g of cyclohexanone with selectivity of 46 percent.

Claims (8)

1. A method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt, characterized in that it comprises the following steps:
dispersing metal porphyrin MOFs PCN-224(Co) and Zn (II) salt in cycloparaffin, wherein the mass of the metal porphyrin MOFsPCN-224(Co) is 0.001% -10% of the mass of the cycloparaffin, and the mass is g/mol; the amount of Zn (II) salt is 0.01-10% of that of cycloalkane, mol/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the metalloporphyrin MOFs PCN-224(Co) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
Figure FDA0002650231920000011
the Zn (II) salt is Zn (CH)3COO)2，Zn(NO3)2，ZnSO4，ZnCl2And hydrates thereof, or a mixture of at least two of the hydrates in any proportion;
the cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
2. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/zn (ii) salts according to claim 1, wherein the catalyst is a binary combination of metalloporphyrin MOFs PCN-224(Co) and zn (ii) salts.
3. The method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt according to claim 1 or 2, wherein the ratio of the mass of the metalloporphyrin MOFs PCN-224(Co) to the amount of cycloalkanes is 1: 100000 to 1: 10.
4. The method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Zn (II) salt according to claim 1 or 2, wherein the mass ratio of Zn (II) salt to cycloalkanes is 1: 10000 to 1: 10.
5. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/Zn (II) salts according to claim 1 or 2, wherein the reaction temperature is 90-150 ℃.
6. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/Zn (II) salts according to claim 1 or 2, wherein the stirring speed is 600-1200 rpm.
7. The process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts, MOFs PCN-224(Co)/zn (ii), according to claim 1 or 2, wherein said oxidant is oxygen, air or a mixture thereof in any proportion.
8. The process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts MOFs PCN-224(Co)/Zn (II) according to claim 1 or 2, wherein said post-treatment is carried out in such a way thatThe method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 3 percent of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061776A (en) * 2015-08-10 2015-11-18 北京工业大学 Metal organic framework material of Fe porphyrin ligand, preparation method therefor and application thereof
CN110563550A (en) * 2019-08-30 2019-12-13 浙江工业大学 Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt
CN110563555A (en) * 2019-08-28 2019-12-13 浙江工业大学 Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061776A (en) * 2015-08-10 2015-11-18 北京工业大学 Metal organic framework material of Fe porphyrin ligand, preparation method therefor and application thereof
CN110563555A (en) * 2019-08-28 2019-12-13 浙江工业大学 Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt
CN110563550A (en) * 2019-08-30 2019-12-13 浙江工业大学 Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt

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